Asymmetric azo dyestuffs of the pyrazolone series and a process of making same



Patented Apr. 25, 1950 2,505,244

UNITED STATES PATENT OFFICE ASYMMETRIC AZO DYESTUFFS OF THE PYRAZOLONE SERIES AND A PROCESS OF MAKING SAME Peter Hindermann, Basel, Switzerland, assignor to J. R. Geigy A. G., Basel, Switzerland No Drawing. Application December 31, 1946, Se-

rial No. 719,634. In Switzerland December 27,

6 Claims. (01. 260-160) I 2 I have found that the metallizable asymmetric As aromatic amines falling within the scope azo dyestuffs of the pyrazolone series of the genof the radical A in the above Formula I may be eral Formula I enumerated unsubstituted or substituted primary wherein aromatic amines; among the latter ones I use preferably those which carry metallizable groups or substituents convertible into such metallizable groups in o-position to the diazotizable amino group. In all of the aromatic amines the alkyl, halogen, hydroxyl, alkoxy, nitro, acylamino, carboxy, carbamino, sulfonic acid groups and so on may be present.

The new method according to the present invention makes possible the production of a large number of new dyestuffs which are distinguished X represents an oxygen or sulfur atom,

Y denotes a methyl, ethyl or phenyl group,

Z denotes a member selected from the group consisting of radicals of the benzene series bound in 1:4-position and of radicals of the diphenyl series bound in 4:4-position and A denotes a radical of an aromatic amine different from the radical of l-diazo-G-nitro-Z-hydroxynaphthalene-4-sulfonic acid,

p ss v y va ua l p p t s- The n w dy by good to very good aflinity for cellulosic fibres. stuffs ca be p pa d according to different The asymmetric disazo dyestuffs built up from methods. Thus, for instance molar quantities of 1 (4' amino phenyl) 3 methyl 5 pymz- 1 diazo 6 ni O 2 hydroxynaphthalene olone-urea are particularly valuable, as the same sulfonic acid and of a different, suitable, diazoare easily available and possess a good aifinity.

tized aromatic amine which may still further be The asymmetric disazo dyestuffs of the general substituted can be combined in h manner Formula I, wherein A denotes the radical of a known fo t preparation of pyrazolone esimple diazotizable amino compound of the naphstuffs in y Order of succession with molar thalene series, the radical of an o-hydroxy, o-alquantities of a dipyrazolone of the following genkoXy or o-carboxy amino compound of the heneral Formula II in a Sli htly acid, n u l zene series which is free from sulfonic acid slightly alkaline medium groups or the radical of a diazotized 4'-acylamino- 00- 4-amin0 compound of the diphenyl series, possess excellent fastness properties in the moist state,

N Z NH 'GX NH Z N if the dyeings on cellulosic fibres have been after- =N treated with copper salts. By a treatment with wherein X, Y and Z have the above significance. 4o metal-yielding agents the new disazo dyestuffs Another method consists, in linking mixtures of can be converted according to known methods amino azo dyestuffs obtainable, on the one hand, into the metal complex compounds. Because of from 1-diazo-6-nitro-2-hydroxynaphthalene-4- their excellent light-fastness the complex copper sulfonic acid, on the other hand from any diazocompounds are particularly valuable. The coptized aromatic amine different from the former pering can be carried out, as known, for instance compound and being further substituted, if dewith copper sulfate in a neutral or slightly acetic sired, as well as of an amino aryl pyrazolone of acid bath or in the presence of tartaric salts in a the general Formula III slightly alkaline bath. The dyestuffs can also be converted in substance according to known methods in an acid, neutral or alkaline medium'by means of the usual copper compounds into com v I plex copper compounds. When treating the dyewherein Y and Z corr'spiondto the above signifistufis of the present invention with copper salts canoe, with phosgene, h fih sgen 1 carbon often the fastness properties to alkalis and in disulfide. i the moist state, beside the light-fastness, W111 be improved. The new dyestuffs dye cellulosic fibres in different shades varying in general from orange, red to red-brown, this depending upon the constitution of the dyestuffs.

The following examples will illustrate how to carry out the new method, without limiting the present invention to the said examples, in which the parts are by weight. Moreover, it may be understood that parts by weight bear the same relationship to parts by volume that grams bear to cubic centimeters. The temperatures are expressed in degrees centigrade.

Example 1 29.5 parts of 1-diazo-6-nitro-2-hydroxynaphthalenel-sulfonic acid are combined, while cool ing with ice, in the presence of an excess of sodiumv carbonate with 40.4 parts of urea of 1-(4'-aminophenyl)-3-methyl-5-pyrazolone in order toproduce the intermediate product. After some hours the formation of the intermediate product is complete. The sodium carbonate present in an excess is treated with hydrochloric acid, until a bicarbonat'ic reaction has been reached, whereupon further coupling is effected with the diazonium compound of 13.7 parts of -methyl-2-methoxy-1- amino-benzene. The disazo dyestuff thus formed is precipitated with sodium chloride, filtered and dried. It constitutes a dark powder which is soluble in water with a dark red-brown coloration and in concentrated sulfuric acid with an orange coloration. The new dyestuff dyes cellulosic fibres from a neutral bath containing Glaubers salt in reddish brown shades which are changed by an after-treatment with copper sulfate into a red coloration distinguished by very good fastness properties to light and in the moist state.

The ufea of 1-(4-am'inop'heny1)-3-methy1-5- pyrazolo'ne can be obtained by introducing phosgene into a solution of 37.8 parts of the said aihifiopyfazol'one in 500' parts of water in the presence of anexcess of sodium carbonate at-room temperature, until no free'amino groups can be detected.

Example 2 295' parts of 1-diazo-6-n'itro-2-hydroxynaph thal'enel-sulfonic acid are combined with 40.4 parts of urea of 1- (4'-aminophenyl) -3- methyl -5- pyra'zolone in the manner described in Example 1, thus giving the monoazo intermediate product. The latter is then coupled in a litmus-neutral medium with the diazo compound from 13.7 parts of Z-amino benzoic acid to give the disazo dyes'tufi, which is isolated by addition of sodium chloride. The new dyestuff is a dark powder, dissolving in water with a dark red-brown coloration and in concentrated sulfuric acid with an orange coloration and dyeing cellulosic fibres in reddish-brown shades. By an after treatment with copper sulfate an orange red shade is produced which is distinguished by very good fastness properties in the moist state and to light.

A dyestuff of similar properties will be obtained, if 17.15 parts of 5-chloro-2-aminobenzoic acid, instead of Z-aminobenzoic acid, are diazotized in the manner described in the above example and worked up otherwise in exactly the same manner.

Example 3 56' parts of aminoazo dyestuif obtainable by coupling diazotized 1-amino-6-nitro-2-hydroxynaphthalene-4-sulfonic acid with 1-phenyl-(4- phenyl-4-amino) -3-methyl-5-pyrazolone and 57.9 parts of the amino azo dyestuif obtainable by coupling diazotized 1-aminonaphthalene-3: 6- disulfom'c acid with 1-phenyl-(4-phenyl-4"- amino) -3-methyl-5-pyrazolone are condensed in 1000 parts of water in the presence of an excess of sodium carbonate at ordinary temperature with phcsgene, until no more free amino groups can be detected. The so-formed asymmetric disazodyestuff is salted out, filtered by suction, and dried. It constitutes a dark powder dissolving in water with a red coloration and in concentrated sulfuric acid with an orange coloration, the new d'yestuff-dyeing cotton and fibres from regenerated celliilose in red-brown shades which are converted into orange shades of good fastness properties inthemoist state and to light, when after-treated with copper salts.

The same dyestuif will be obtained, if 29.5 parts of 1-diazo-6 nitro z-hydroxy-naphthalene-4-sulfonic' acid are combined with 55.6 parts of urea of 1 phenyl (4 phenyl-4"-amino) -3-methyl-5- pyrazolone to give the intermediate product and if the latter is further coupled with the diazo compound obtainable from 30.3 parts of l-aminonapthalene-3:6-disulfonie acid.

The urea of l-phenyl- (4-phenyl:4 -amino) -3- methy1-5-pyrazolone is obtained by introducing phosgene into a solution of 53 parts of the said aminopyrazo-lone in 500 parts of water inthe pres ence of an excess of sodium carbonate at room temperature, until no more free am-i-no groups can be detected.

Example 4 29.5 parts of l diam-=6 nitro 2 hydroxynaphthalenel-sulfonic acid are combined as indicated in Example 1 with 40.4 parts of urea of 1-(4'-amino-phenyl) -3-methy1-5'-pyrazo1sne, thus giving the intermediate pinch t. The resulting monoazo dyestu'fl is coupled in a neutral to litmus with the diaz'onium coin-pound from 14.3 parts of 2-aminonaphthalene in order to produce thedisazo dyestuff, which is isolated by means of sodium chloride. The" new dyestu-ff constitutes a dark powder dissolvingin water with a red-brown coloration and in concentrated sulfuric acid with anorangecoloration;- it dyes cellulosic fibres in reddish-brown shades. By an after-treatment with copper salts a red coloration is obtained, Whose dyein gs possess a very good light f'astness and very good fastness propertiesin the moist state.

A dyestufi of similar properties will be obtained, if in the above example, instead of 2-arninonaphthalene, 14.3 parts of l-aminonaphthalene are diazotized and worked up in exactly the same manner.

Exam le 5 2 9.5 parts of 1-diazo-6-nitro-2-hydroxynaphthalene-l-sulfonic acid are combined according to Example 1 with 40.4 parts of urea of 1-(4'- aminophen'yl)-3-methy1-5-pyrazolone; thus giving the monoazo dyestuff, which is then further coupled in a litmus-neutral medium to the disazo dyestufi" by means of the diazonium compound from 18.7 parts of 2 aminonaphthalene-3-carboxylic acid. The disazodyestuff is isolated by addition of sodium chloride, then filtered by suction and dried. The so-obtained disazo dyestuff which is a dark powder is soluble inwater with a brownish-red colorationandin concentrated sulfuric acid with an orangecoloration and dyes fibres from regenerated cellulose in reddishbrown shades. By an after treatment with copper sulfate these shades are converted into red shades of good fastness properties to light and in the moist state.

Exampl'e'fi' 29.5 parts of 1-diazo-6-nitro-2-hydroxynaphmethyl--pyrazolone in the presence of an excess of sodium carbonate, thus giving the mo-noazo dyestuff. After stirring for several hours while cooling with ice the diazo compound has disappeared. Then the excess of sodium carbonate is treated with hydrochloric acid, until the bicarbonatic stage has been reached, whereupon the mixture is further coupled with the diazonium compound from 9.3 parts of l-aminobenzene. The resultant disazo dyestuff is isolated by addition of sodium chloride, filtered by suction and dried. It constitutes a dark powder which is soluble in water with a brownish-red coloration and in concentrated sulfuric acid with an orange coloration. The new dyestuff dyes cotton and cellulosic fibres in brownish-red shades which are changed into red shades of very good fastness properties, when subjected to an after-treatment with copper salts.

The thiourea of 1-(4 aminophenyl) 3- methyl-5-pyrazolone can be made by treating 37.8 parts of 1-(4-aminophenyl)-3-methyl-5- pyrazolone in 500 parts of water with thiophosgene in the presence of an excess of sodium carbonate, until no more free amino groups can be detected, or by condensing 1 4 aminophenyl)-3-methyl-5-pyrazolone with carbon disulfide in the presence of small quantities of hydrogen peroxide, until no more free amino groups can be detected.

Instead of the diazo compound from 9.3 parts of l-aminobenzene, there may be used the diazo compounds from 18.2 parts of 5-nitro-2-aminobenzoic acid, 13.7 parts of 5-methyl-2-methoxyl-aminobenzene, 14.3 parts of Z-aminonaphthalene, 22.6 parts of 4-amino-4'-acetylaminodiphenyl, 13.35 parts of 5-chloro-2-hydroXy-1- aminobenzene or 30.8 parts of 6-benzoylamino- 2-amino-l-hydroxybenzene-4-sulfonic acid, the procedure being essentially the same as described in the above example.

Example 7 29.5 parts of 1 diazo 6 nitro 2 hydroxynaphthalene-4-sulfonic acid are combined according to Example 1 with 40.4 parts of urea of 1- (4 aminophenyl) 3-methyl-5-pyrazolone, thus giving the monoazo dyestuff, which is then further coupled in a litmus-neutral medium to the disazo dyestufi by means of the diazonium compound from 22.6, parts of 4-amino-4'-acetylaminodiphenyl. The so-obtained dyestuff is isolated by addition of sodium chloride, then filtered by suction and dried and represents a dark powder, which is soluble in water with an orangered coloration and in concentrated sulfuric acid with an orange coloration. The new dyestuff dyes cellulosic fibres in brownish-red shades which become orangeish-red on after-treatment with copper-sulfate, the fastness properties in the moist state and to light becoming thus substantially improved.

A dyestuif having similar properties will be ob tained, when diazotizing, as described in the above example, 29.5 parts of 3:3'-dichloro-4- amino-A-acetylaminodiphenyl, instead of 4- amino-4-acetylaminodiphenyl, the procedure being essentially the same as described in the above example.

Example 8 29.5 parts of l-diazo-6-nitro-2-hydroxynaphthalene-4-sulfonic acid are combined with 43.2 parts of urea of 1-(4-amino-2'-methylphenyl)- 3-methyl-5-pyrazolone in the presence of an excess of sodium carbonate, while cooling with ice, thus givin the intermediate product, which is completed after some hours. The excess of sodium carbonate is removed by means of hydrochloric acid, until a bicarbonatic reaction has been reached, whereupon the intermediate product is further coupled with the diazonium compound of 13.35 parts of 5-chloro-2-hydroxy-laminobenzene. The disazo dyestufi thus formed is precipitated by addition of sodium chloride, filtered and dried. It is a dark powder which is soluble in water with a brown-red coloration and in concentrated sulfuric acid with an orange coloration and dyes cellulosic fibres from a neutral dye bath containing Glaubers salt in reddishbrown shades which become red by an aftertreatment with copper sulfate, the resulting red shades being distinguished by very good fastness properties to light and in the moist state.

The urea of 1-(4-amino-2'-methylphenyl)-3- methyl-5-pyrazolone is produced by introduction of phosgene into a solution containing 40.6 parts of the above said aminopyrazolone in 500 parts of water in the presence of an excess of sodium carbonate, this procedure being carried out at room temperature until no more free amino groups are present.

1 (F-amino 2 methylphenyl) -3-methyl-5- pyrazolone is obtained from 13 parts of acetoacetic acid ethyl ester by interaction with 16.? parts of 4-nitro-2-methylphenylhydrazine in boiling alcohol, whereby first the corresponding 1 (4' nitro-2-methylphenyl)-3-methyl-5-pyrazolone is produced which by reduction with iron is converted into the above said amino pyrazolone.

When causing other acyl acetic esters or substituted p-nitrophenylhydrazines to react with each other in equivalent quantities, the corresponding 1 (4'-nitrophenyl) -5-pyrazolones or 1-(4' aminophenyl) -5-pyrazolones respectively will be produced, which products have similar Table shade of the No. diazo compound dipyrszolone according to Formula II A-aromatlc amine m gg g gf losic fibres may from- I 1 l.. l-dlazo-6-nitrw2-hydroxynaphtha- 1-(4'-ainlnophenyl-3-methyl-5-pyrazo- .5-nitro-2-emino-benzoic acid orange.

lene-i-sulionic acid. ne. 1 2 do 1-(4-aminophenyl)-3-phenyl-5-pyrazolo- Z-chloro-l-eminobenzene red.

ne. 3 .-do 1-(l4'-aminophenyl)-3-methyl-5-pyrazo- 4-chloro-1-aminobenzene Do,

one.

4. The metallizab le disazo dyestufi which, in wherein A stands for a radical of the benzene the free state, corresponds to the formula 5. A metallizable disazo dyestuff which, in the series free from sulfonic acid groups, which free state, corresponds to the formula comprises coupling 1 mole of 1-diazo-6-nitr0-2- hydroxy-naphtha1ene-4-sulfonic acid with 1 mole of the pyrazolone-urea of the formula wherein A stands for a radical of the benzene25 series free from sulfoni acid groups. 3- O 6. A process for the manufacture of a metailizable disazo dyestufi which, in the free state, cor- H: H:

responds to the formula 30 and coupling the so-obtained monoazo dyestufl with 1 mole of a diazotized amine of the benzene series free from 'sulfonic acid groups.

PETER HINDERMANN.

REFERENCES CITED The following references are of record in the file of this patent:

UNITED STATES PATENTS Number Name Date 1,845,426 Latten Feb. 16, 1932 2,185,901 Schmid Jan. 2, 1940 2,195,784 Schmid Apr. 2, 1940 2,195,787 Schmid Apr. 2, 1940 2,195,788 Schmid Apr. 2, 1940 2,221,360 Schmid Nov. 12, 1940 2,221,361 Schmid Nov. 12, 1940 I 2,228,374 Stusser Jan. 14, 1941 

1. PROCESS FOR THE MANUFACTURE OF A METALLIZABLE DISAZO DYESTUFF WHICH, IN THE FREE STATE, CORRESPONDS TO THE FORMULA 